U.S. patent application number 16/647174 was filed with the patent office on 2020-07-30 for method for directly producing methyl acetate and/or acetic acid from syngas.
This patent application is currently assigned to DALIAN INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES. The applicant listed for this patent is DALIAN INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES. Invention is credited to Hongchao LIU, Shiping LIU, Yong LIU, Zhongmin LIU, Xiangang MA, Youming NI, Fuli WEN, Wenliang ZHU.
Application Number | 20200239401 16/647174 |
Document ID | 20200239401 / US20200239401 |
Family ID | 1000004765248 |
Filed Date | 2020-07-30 |
Patent Application | download [pdf] |
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United States Patent
Application |
20200239401 |
Kind Code |
A1 |
LIU; Hongchao ; et
al. |
July 30, 2020 |
METHOD FOR DIRECTLY PRODUCING METHYL ACETATE AND/OR ACETIC ACID
FROM SYNGAS
Abstract
A method for directly producing methyl acetate and/or acetic
acid from syngas, carried out in at least two reaction zones,
including: feeding a raw material containing syngas into a first
reaction zone to contact and react with a metal catalyst; allowing
an obtained effluent to enter a second reaction zone directly or
after the addition of carbon monoxide so as to contact and react
with a solid acid catalyst; separating the obtained effluent to
obtain product of acetate and/or acetic acid, and optionally
returning a residual part to enter the first reaction zone and/or
the second reaction zone to recycle the reaction. This provides a
novel method for directly converting syngas into methyl acetate
and/or acetic acid. Further, the product selectivity of the product
of methyl acetate or acetic acid is greater than 93%, and the
quantity of methyl acetate and acetic acid may be adjusted
according to processing.
Inventors: |
LIU; Hongchao; (Dalian,
CN) ; ZHU; Wenliang; (Dalian, CN) ; LIU;
Zhongmin; (Dalian, CN) ; LIU; Yong; (Dalian,
CN) ; LIU; Shiping; (Dalian, CN) ; WEN;
Fuli; (Dalian, CN) ; NI; Youming; (Dalian,
CN) ; MA; Xiangang; (Dalian, CN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
DALIAN INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF
SCIENCES |
Dalian |
|
CN |
|
|
Assignee: |
DALIAN INSTITUTE OF CHEMICAL
PHYSICS, CHINESE ACADEMY OF SCIENCES
Dalian
CN
|
Family ID: |
1000004765248 |
Appl. No.: |
16/647174 |
Filed: |
September 29, 2017 |
PCT Filed: |
September 29, 2017 |
PCT NO: |
PCT/CN2017/104609 |
371 Date: |
March 13, 2020 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B01J 23/002 20130101;
B01J 29/40 20130101; C07C 51/10 20130101; B01J 23/8892 20130101;
B01J 29/18 20130101; B01J 29/70 20130101; B01J 2208/025 20130101;
B01J 8/065 20130101; B01J 29/7023 20130101; C07C 67/36 20130101;
B01J 8/0492 20130101 |
International
Class: |
C07C 67/36 20060101
C07C067/36; C07C 51/10 20060101 C07C051/10; B01J 8/04 20060101
B01J008/04; B01J 8/06 20060101 B01J008/06; B01J 23/889 20060101
B01J023/889; B01J 23/00 20060101 B01J023/00; B01J 29/40 20060101
B01J029/40; B01J 29/18 20060101 B01J029/18; B01J 29/70 20060101
B01J029/70 |
Claims
1-8. (canceled)
9. A method for directly producing methyl acetate and/or acetic
acid from syngas, whose reaction process is carried out in at least
two reaction zones, the method comprising: a) feeding a raw
material containing syngas into a first reaction zone to contact
with a metal catalyst in the first reaction zone, reacting to
obtain an effluent containing methanol and/or dimethyl ether; b)
allowing the effluent from the first reaction zone to enter a
second reaction zone directly or after the addition of carbon
monoxide so as to contact with a solid acid catalyst in the second
reaction zone and react to obtain an effluent containing methyl
acetate and/or acetic acid; and c) separating the effluent from the
second reaction zone to obtain product of acetate and/or acetic
acid, and optionally returning a residual part to enter the first
reaction zone and/or the second reaction zone to recycle the
reaction; wherein the volume content of syngas feed gas in the raw
material is in a range from 10% to 100%, and the volume ratio of
carbon monoxide to hydrogen in the syngas is in a range from 0.1 to
10; and the reaction temperature in the first reaction zone is in a
range from 180.degree. C. to 300.degree. C., the reaction pressure
is in a range from 0.5 MPa to 20.0 MPa; and the reaction
temperature in the second reaction zone is in a range from
180.degree. C. to 300.degree. C., the reaction pressure is in a
range from 0.5 MPa to 20.0 MPa.
10. The method of claim 9, wherein the metal catalyst in the first
reaction zone is a catalyst for synthesis of methanol or dimethyl
ether.
11. The method of claim 9, wherein the solid acid catalyst in the
second reaction zone comprises one or more molecular sieves
selected from FER, MFI, MOR, ETL, MFS, MTF, EMT zeolite molecular
sieves and molecular sieve products obtained by modifying the
zeolite molecular sieves using pyridine or elements other than the
framework constituent elements.
12. The method of claim 11, wherein the solid acid catalyst is a
hydrogen-type product of the zeolite molecular sieve, or ranges
from 10% to 95% by weight of the hydrogen-type product and a
remaining matrix, or is a molecular sieve product obtained by
modifying of the hydrogen-type product with pyridine, wherein the
matrix is one or more selected from alumina, silica, kaolin and
magnesia.
13. The method of claim 9, wherein the first reaction zone and/or
the second reaction zone are in a fixed bed reactor.
14. The method of claim 9, wherein the first reaction zone and the
second reaction zone are in the same fixed reactor, or the first
reaction zone and the second reaction zone are respectively in
different reactors connected in series.
15. The method of claim 9, wherein the syngas in the raw material
ranges from 50% to 100% by volume of carbon monoxide and hydrogen
and ranges from 0% to 50% by volume of one or more inactive gases
selected from nitrogen, helium, argon and carbon dioxide.
16. The method of claim 9, wherein the reaction temperature in the
first reaction zone is in a range from 190.degree. C. to
290.degree. C. and the reaction pressure is in a range from 1.0 MPa
to 15.0 MPa; and the reaction temperature in the second reaction
zone is in a range from 190.degree. C. to 290.degree. C. and the
reaction pressure is in a range from 1.0 MPa to 15.0 MPa.
17. The method of claim 13, wherein the fixed bed reactor is a
tubular fixed bed reactor.
Description
TECHNICAL FIELD
[0001] The present invention relates to a method for directly
converting syngas to produce methyl acetate and/or acetic acid.
BACKGROUND
[0002] Methyl acetate is a colorless, scented liquid with less
toxicity and strong dissolving ability, which is an excellent
cellosolve and spray solvent. As an important intermediate in the
chemical industry, methyl acetate can produce downstream products
including ethanol, acetic acid, acetic anhydride, methyl acrylate,
vinyl acetate, and acetamide, etc., and have a very broad
application prospect.
[0003] Acetic acid is an important organic acid, which can be used
in the production of vinyl acetate, acetic anhydride, cellulose
acetate, acetates and metal acetates. Acetic acid is also used as a
solvent and raw material in pesticides, pharmaceuticals and dyes
and other industries. Acetic acid is widely used in pharmaceutical
manufacturing, textile printing and rubber industries.
[0004] At present, the main synthesis methods of methyl acetate
are: reactive distillation of methanol and acetic acid as raw
materials; methanol dehydrogenation synthesis of methanol as raw
material; one-step methanol carbonylation method of methanol and CO
as raw materials; homologation of methyl formate and dimethyl ether
carbonylation. The industrial production method of acetic acid is
mainly carbonylation of methanol on Rh--I or Ir--I catalyst to
generate acetic acid. Because this process uses precious metal
catalysts, and there is also the production of hydrogen halide, the
requirements for production equipment are extremely high.
[0005] The production of a large variety of basic chemical raw
materials and high value-added fine chemicals using syngas as raw
materials has been a hot topic in the field of catalysis. The
direct preparation of ethanol from syngas is a new process for
ethanol preparation in recent years. From the point of view of
process and cost, the process of direct preparation of ethanol from
syngas is short, the operating cost is relatively economical, and
the investment cost is low. However, from the perspective of
thermodynamics and kinetics, it is difficult for the reaction to
stay on the target product, i.e. ethanol. Because the direct
preparation of ethanol from syngas is a strong exothermic reaction,
the first problem is to solve the problems of selectivity and
tolerance. From the actual reaction results, the products are
widely distributed. Not only there are a large number of C2
oxygenated by-products such as acetaldehyde and acetic acid, but
also C2-C5 alkanes and olefins. The selectivity of ethanol is not
ideal and the yield is low.
[0006] Although the rhodium-based catalyst has the performance of
selectively synthesizing C2 oxygenated compounds by syngas.
However, the use of precious metal such as rhodium has greatly
increased the production cost of ethanol, and the production of
rhodium is limited. There is great difficulty in large-scale
promotion and application, which has become the bottleneck of the
industrialization of this process route. Significantly reducing the
use of rhodium or replacing rhodium with non-precious metal
catalysts is an effective way to promote the industrialization of
this technology, but progress is currently relatively slow.
[0007] Dalian Institute of Chemical Physics discloses a method for
producing methyl acetate by carbonylation of dimethyl ether and
carbon monoxide-containing feed gas in a reactor carrying an acidic
EMT zeolite molecular sieve as a catalyst (CN106365995A). According
to the relevant technology of Dalian Institute of Chemical Physics,
a 100,000 ton coal-based ethanol project industrial demonstration
project has been successfully put into operation and runs stably.
However, the direct production of oxygenated compounds using syngas
as the raw material has always been the focus of researchers. The
invention uses syngas as the raw material to provide a new method
for direct synthesis of methyl acetate and/or acetic acid from
syngas, with high product selectivity, mild reaction conditions,
simple process, and has great industrial application prospects.
SUMMARY OF THE INVENTION
[0008] The purpose of the present invention is to overcome some or
all of the problems in the prior art, and provide a novel
technology for syngas conversion and a novel method for the
production of methyl acetate and acetic acid.
[0009] To this end, the present invention provides a method for
directly producing methyl acetate and/or acetic acid from syngas,
whose reaction process is carried out in at least two reaction
zones and the method comprises:
[0010] a) feeding a raw material containing syngas into a first
reaction zone to contact with a metal catalyst in the first
reaction zone, reacting to obtain an effluent containing methanol
and/or dimethyl ether;
[0011] b) allowing the effluent from the first reaction zone to
enter a second reaction zone directly or after the addition of
carbon monoxide so as to contact with a solid acid catalyst in the
second reaction zone and react to obtain an effluent containing
methyl acetate and/or acetic acid;
[0012] c) separating the effluent from the second reaction zone to
obtain product of acetate and/or acetic acid, and optionally
returning a residual part to enter the first reaction zone and/or
the second reaction zone to recycle the reaction;
[0013] wherein the volume content of syngas feed gas in the raw
material is in a range from 10% to 100%, and the volume ratio of
carbon monoxide to hydrogen in the syngas is in a range from 0.1 to
10;
[0014] the reaction temperature in the first reaction zone is in a
range from 180.degree. C. to 300.degree. C., the reaction pressure
is in a range from 0.5 MPa to 20.0 MPa; and the reaction
temperature in the second reaction zone is in a range from
180.degree. C. to 300.degree. C., the reaction pressure is in a
range from 0.5 MPa to 20.0 MPa.
[0015] Preferably, the metal catalyst in the first reaction zone is
a catalyst for synthesis of methanol or dimethyl ether.
[0016] Preferably, the solid acid catalyst in the second reaction
zone comprises one or more molecular sieves selected from FER, MFI,
MOR, ETL, MFS, MTF, EMT zeolite molecular sieves and molecular
sieve products obtained by modifying the zeolite molecular sieves
using pyridine or elements other than the framework constituent
elements.
[0017] Preferably, the solid acid catalyst is a hydrogen-type
product of the zeolite molecular sieve, or is composed of ranging
from 10% to 95% by weight of the hydrogen-type product and a
remaining matrix, or is a molecular sieve product obtained by
modifying the hydrogen-type product with pyridine; wherein the
matrix is one or more selected from alumina, silica, kaolin and
magnesia.
[0018] Preferably, the first reaction zone and/or the second
reaction zone are in a fixed bed reactor, and the fixed bed reactor
is preferably a tubular fixed bed reactor.
[0019] Preferably, the first reaction zone and the second reaction
zone are in the same fixed reactor, or the first reaction zone and
the second reaction zone are respectively in different reactors
connected in series.
[0020] Preferably, the syngas in the raw material is composed of
ranging from 50% to 100% by volume of carbon monoxide and hydrogen
and ranging from 0% to 50% by volume of one or more inactive gases
selected from nitrogen, helium, argon and carbon dioxide.
[0021] Preferably, the reaction temperature in the first reaction
zone is in a range from 190.degree. C. to 290.degree. C. and the
reaction pressure is in a range from 1.0 MPa to 15.0 MPa; and the
reaction temperature in the second reaction zone is in a range from
190.degree. C. to 290.degree. C. and the reaction pressure is in a
range from 1.0 MPa to 15.0 MPa.
[0022] The present invention includes but is not limited to the
following beneficial effects:
[0023] 1. This is provided a novel method for direct and
directional synthesis of methyl acetate and/or acetic acid from
syngas.
[0024] 2. The method of the present invention has high product
selectivity, mild reaction conditions, simple process, and has
great industrial application prospects.
BRIEF DESCRIPTION OF THE DRAWINGS
[0025] FIG. 1 is a flow chart of the direct preparation of methyl
acetate/acetic acid from syngas according to an embodiment of the
present invention, wherein the first reaction zone and the second
reaction zone are in the same reactor.
[0026] FIG. 2 is a flow chart of the direct preparation of methyl
acetate/acetic acid from syngas according to another embodiment of
the present invention, wherein the first reaction zone and the
second reaction zone are in different reactors.
DETAILED DESCRIPTION OF THE EMBODIMENT
[0027] Through the coupling of the catalyst and the novel reaction
process, the present invention enables the syngas to use
non-precious metal catalysts and molecular sieve catalysts to
selectively produce methyl acetate and/or acetic acid under certain
conditions, greatly simplifying the process of carbonylation to
produce methyl acetate and/or acetic acid, reducing the production
and operation costs, while opening up a novel method of direct
syngas conversion.
[0028] The present invention provides a method for directly
producing methyl acetate and/or acetic acid from syngas. The syngas
raw material was passed through a reactor equipped with a metal
catalyst such as a copper-based catalyst and a solid acid catalyst
such as an acidic molecular sieve catalyst. Methyl acetate and/or
acetic acid were produced under the conditions of a reaction
temperature of ranging from 190.degree. C. to 290.degree. C., a
reaction pressure of ranging from 0.5 MPa to 20.0 MPa and a space
velocity of ranging from 1500 h.sup.-1 to 20000 h.sup.-1.
[0029] The method of the present invention includes the following
processes: contacting a gaseous material containing syngas with a
metal catalyst in a first reaction zone and reacting to obtain an
effluent containing methanol and/or dimethyl ether; directly
contacting the reaction effluent with a solid acid catalyst in the
second reaction zone and reacting, or contacting the reaction
effluent where was added a raw material gas containing carbon
monoxide with a solid acid catalyst in the second reaction zone and
reacting. After the reaction, an oxygenate product containing
methyl acetate and/or acetic acid is obtained, and the product
selectivity of the product methyl acetate or acetic acid is higher
than 93%.
[0030] More specifically, in the method for directly producing
methyl acetate and/or acetic acid from syngas, whose reaction
process is carried out in at least two reaction zones and the
method comprises:
[0031] a) feeding a raw material containing syngas into a first
reaction zone to contact with a metal catalyst in the first
reaction zone, reacting to obtain an effluent containing methanol
and/or dimethyl ether;
[0032] b) allowing the effluent from the first reaction zone to
enter a second reaction zone directly or after the addition of
carbon monoxide so as to contact with a solid acid catalyst in the
second reaction zone and react to obtain an effluent containing
methyl acetate and/or acetic acid;
[0033] c) separating the effluent from the second reaction zone to
obtain product of acetate and/or acetic acid, and optionally
returning a residual part to enter the first reaction zone and/or
the second reaction zone to recycle the reaction;
[0034] wherein the volume content of syngas feed gas in the raw
material is in a range from 10% to 100%, and the volume ratio of
carbon monoxide to hydrogen in the syngas is in a range from 0.1 to
10;
[0035] the reaction temperature in the first reaction zone is in a
range from 180.degree. C. to 300.degree. C., the reaction pressure
is in a range from 0.5 MPa to 20.0 MPa; and the reaction
temperature in the second reaction zone is in a range from
180.degree. C. to 300.degree. C., the reaction pressure is in a
range from 0.5 MPa to 20.0 MPa.
[0036] In the method of the present invention, the metal catalyst
in the first reaction zone is a catalyst for synthesis of methanol
or dimethyl ether.
[0037] In the method of the present invention, preferably, the
solid acid catalyst in the second reaction zone comprises any one
or any combination of zeolite molecular sieves of FER, MFI, MOR,
ETL, MFS, MTF or EMT structures, or products obtained by modifying
elements other than the constituent elements (such as Fe, Ga, Cu,
Ag, etc.) of molecular sieve framework that meets the above
characteristics or by modifying pyridine, or a mixture of multiple
molecular sieves that meet the above characteristics.
[0038] Preferably, the solid acid catalyst is a hydrogen-type
product of the zeolite molecular sieve, or is composed of ranging
from 10% to 95% by weight of the hydrogen-type product and a
remaining matrix, or is a molecular sieve product obtained by
modifying the hydrogen-type product with pyridine; more preferably;
the matrix is any one or a mixture of any one of alumina, silica,
kaolin and magnesia.
[0039] In the method of the present invention, preferably, reactors
for the first reaction zone and the second reaction zone each adopt
a fixed bed reactor, preferably a tubular fixed bed reactor.
[0040] In the method of the present invention, the first reaction
zone and the second reaction zone may be in the same reactor, or
the first reaction zone and the second reaction zone may be in
different reactors connected in series.
[0041] In the method of the present invention, in addition to
carbon monoxide and hydrogen, the syngas raw material may also
contain any one or more inactive gases selected from nitrogen,
helium, argon and carbon dioxide. Preferably, the volume content of
carbon monoxide and hydrogen is in a range from 50% to 100%; the
volume percentage content of any one or more gases selected from
nitrogen, helium, argon and carbon dioxide in the syngas raw
material is in a range from 0% to 50%.
[0042] In a further preferred embodiment, the reaction conditions
in the first reaction zone are as follows: the reaction temperature
is in a range from 180.degree. C. to 300.degree. C., the reaction
pressure is in a range from 1.0 MPa to 15.0 MPa; the reaction
conditions in the second reaction zone are as follows: the reaction
temperature is in a range from 180.degree. C. to 300.degree. C.,
the reaction pressure is in a range from 1.0 MPa to 15.0 MPa.
[0043] The present invention is specifically illustrated by the
following examples, but the present invention is not limited to
these examples.
Metal Catalyst
[0044] The metal catalyst was a copper-based catalyst, which was
prepared as follows: in a beaker, 96.80 g of
Cu(NO.sub.3).sub.2.3H.sub.2O, 15.60 g of
Zn(NO.sub.3).sub.2.6H.sub.2O, and 14.71 g of
Al(NO.sub.3).sub.3.9H.sub.2O were dissolved in 2000 ml of deionized
water, a mixed metal nitrate aqueous solution was obtained. In
another beaker, 72.62 g of strong ammonia water (25-28%) was
diluted with 1500 ml of deionized water, and the ammonia solution
was vigorously stirred at room temperature, and then the obtained
mixed metal nitrate aqueous solution was slowly added to the
ammonia solution, the addition time was about 60 min. It was
filtered to obtain a precipitate, and the pH value of the
precipitate was adjusted to 10.0 with another aqueous ammonia
solution. After stirring for 200 minutes, it was left to age for 36
hours. Then, the precipitate was washed with deionized water to
neutrality, and centrifuged. The obtained precipitate was dried in
an oven at 120.degree. C. for 24 hours. The dried sample was placed
in a muffle furnace, heated to 400.degree. C. at a temperature
increase rate of 1.degree. C./min, and roasted for 5 hours to
obtain a roasted sample. 1.41 g of Mn(NO.sub.3).sub.2.4H.sub.2O and
1.36 g of Ni(NO.sub.3).sub.2.4H.sub.2O were then dissolved in 50 ml
of deionized water, and the aqueous solution of manganese and
nickel was loaded on the roasted sample by the dipping method, and
evaporated at 80.degree. C. to remove excess solvent. It was dried
in an oven at 120.degree. C. for 24 hours. After drying, the sample
was placed in a muffle furnace, heated to 400.degree. C. at a
heating rate of 1.degree. C./min, and calcined for 3 hours to
obtain a catalyst sample, which was recorded as catalyst A.
[0045] The metal catalyst used in the present invention can also be
prepared by mechanically mixing catalyst A and nano-hydrogen type
ZSM-5 (Si/Al=19) at a ratio of 2:1, which was recorded as catalyst
B.
Raw Material Source of Molecular Sieve
[0046] In the course of the experiment, part of the molecular sieve
materials can be directly purchased commercially; part of the
molecular sieve materials can be synthesized according to existing
related literatures, and the specific sources are shown in Table
1.
TABLE-US-00001 TABLE 1 Sources of different molecular sieve
materials and ratio of silicon-aluminum Molecular sieve material
Source Way of obtaining Si/Al ratio NaMOR (mordenite) The Catalyst
Plant of Nankai University purchase 6.5 NaMOR (mordenite) The
Catalyst Plant of Nankai University purchase 15 NaSM-35 The
Catalyst Plant of Aoke purchase 79 NaZSM-5 The Catalyst Plant of
Nankai University purchase 50 NaEMT Dalian Institute of Chemical
Physics. synthesis 4 NaEMT Dalian Institute of Chemical Physics.
synthesis 25 Na-EU-12 Dalian Institute of Chemical Physics.
synthesis 10 Na-MCM-65 Dalian Institute of Chemical Physics.
synthesis 50 Na-MCM-35 Dalian Institute of Chemical Physics.
synthesis 100 Na-M-MOR* Dalian Institute of Chemical Physics.
synthesis 16.5 *Na-M-MOR represents mordenite modified by elements
other than the framework constituent elements prepared by in-situ
synthesis, wherein M represents a modified metal atom, and the
molecular sieve modified by Fe, Ga, Cu, and Ag metals are prepared
during the preparation process respectively, wherein the content of
the modified metal is 0.9%.
Solid Acid Catalyst
[0047] The hydrogen-type sample was prepared as follows:
[0048] The Na-type molecular sieve in Table 1 were subjected to
NH.sub.4NO.sub.3 ion exchange, dried and roasted to obtain
hydrogen-type molecular sieve. For example, a preparation process
for a typical hydrogen-type sample is as follows: in a hydrothermal
synthesis kettle, NaMOR molecular sieve powder is added to a
pre-configured 1 mol/L NH.sub.4NO.sub.3 aqueous solution with a
solid-liquid mass ratio of 1:10, and was exchanged for 2 hours at
80.degree. C. in the stirring state, filtered under vacuum and
washed with water. After three consecutive exchange reactions, it
was dried at 120.degree. C. overnight and calcined for 4 hours at
550.degree. C. to obtain the required catalyst sample HMOR.
[0049] Matrix-containing shaped hydrogen-type samples were prepared
by extrusion molding. For example, the preparation process for a
typical shaped sample is as follows: 80 g of Na-MOR and 20 g of
alumina were thoroughly mixed, and 5-15% nitric acid was added to
knead. The sample that was kneaded into a ball was extruded and
shaped by an extruder. The extruded sample was dried at 120.degree.
C., and calcined at 550.degree. C. for 4 hours, and then a
hydrogen-type sample preparation method was used to prepare
matrix-containing shaped hydrogen-type samples.
[0050] Pyridine-modified hydrogen-type samples were prepared. The
typical preparation process was as follows: 10 g of hydrogen-type
sample was charged into a reaction tube, and gradually heated to
300-550.degree. C. under a nitrogen atmosphere of 100 mL/min,
maintained for 2-6 hours, and then carried pyridine with nitrogen
and treated at 200-400.degree. C. for 2-8 hours, to obtain pyridine
modified samples. The samples were labeled with H-M-py, where M
represents the name of the molecular sieve.
[0051] The series of samples prepared according to the above
methods are shown in Table 2.
TABLE-US-00002 TABLE 2 The number of the prepared sample and
composition of the sample Catalyst Si/Al ratio of Molecular Matrix
Matrix No. Catalyst molecular sieve sieve content type content 1#
H-MOR 6.5 100% -- 0% 2# H-MOR 6.5 50% silica + 50% alumina +
magnesia (mass ratio 2:2:1) 3# H-MOR 15 80% alumina 20% 4# H-ZSM-35
79 80% kaolin 20% 5# H-ZSM-5 50 70% alumina 30% 6# H-EMT 4 80%
alumina 20% 7# H-EMT 25 80% alumina 20% 8# H-EU-12 10 80% alumina
20% 9# H-MCM-65 50 80% alumina 20% 10# H-MCM-35 100 90% alumina 10%
11# H-MOR-py 15 80% alumina 20% 12# H-EMT-py 25 80% alumina 20% 13#
H-Fe-MOR 16.5 100 -- 0% 14# H-Cu-MOR 16.5 100 -- 0% 15# H-Ag-MOR
16.5 100 -- 0% 16# H-Ga-MOR 16.5 100 -- 0%
Comparative Example 1
[0052] 1 g of catalyst A was charged into a fixed bed reactor with
an inner diameter of 16 mm, and the temperature was raised to
260.degree. C. under a 5 vol % H.sub.2+95 vol % N.sub.2 atmosphere
for 24 hours, and then the temperature was lowered to 220.degree.
C. The pressure of the reaction system was raised to 5 MPa with
H.sub.2 and CO. The flow rate under standard conditions of CO was
30 mL/min and the flow rate under standard conditions of H.sub.2
was 60 mL/min. The results of the catalytic reaction were shown in
Table 3.
Comparative Example 2
[0053] 1 g of catalyst B was charged into a fixed bed reactor with
an inner diameter of 16 mm, and the temperature was raised to
260.degree. C. under a 5 vol % H.sub.2+95 vol % N.sub.2 atmosphere
for 24 hours, and then the temperature was lowered to 220.degree.
C. The pressure of the reaction system was raised to 5 MPa with
H.sub.2 and CO. The flow rate under standard conditions of CO was
30 mL/min and the flow rate under standard conditions of H.sub.2
was 60 mL/min. The results of the catalytic reaction were shown in
Table 3.
Comparative Example 3
[0054] 1 g of molecular sieve catalyst was charged into a fixed bed
reactor with an inner diameter of 16 mm, and the temperature was
raised to 240.degree. C. under a 5 vol % H.sub.2+95 vol % N.sub.2
atmosphere for 24 hours, and then the temperature was lowered to
220.degree. C. The pressure of the reaction system was raised to 5
MPa with H.sub.2 and CO. The flow rate under standard conditions of
CO was 30 mL/min and the flow rate under standard conditions of
H.sub.2 was 60 mL/min. The results of the catalytic reaction were
shown in Table 3.
TABLE-US-00003 TABLE 3 The results of comparative examples Percent
Selectivity for products (%) Comparative conversion Dimethyl Methyl
Acetic example of CO (%) CO.sub.2 Methanol ether acetate acid
Others 1 27.32 0 99.87 0 0 0 0.13 2 38.67 30.94 0.42 67.38 0 0 1.26
3 0 0 0 0 0 0 0
Example 1
[0055] The first reaction zone and the second reaction zone were
located in the same reactor, the specific reaction scheme was shown
in FIG. 1, wherein the syngas as a raw material was allowed to
enter the first reaction zone I to contact with the metal catalyst
in the first reaction zone and react to obtain an effluent
containing methanol and/or dimethyl ether; the effluent from the
first reaction zone was allowed to enter the second reaction zone
II to contact with the solid acid catalyst in the second reaction
zone and react to obtain an effluent containing methyl acetate
and/or acetic acid; the effluent from the second reaction zone was
separated to obtain product of acetate and/or acetic acid; the
residual part was returned to enter the first reaction zone to
recycle the reaction.
[0056] 1 g of copper-based catalyst A and 1 g of solid acid
catalyst 11# were successively charged into the first reaction zone
I (upper end) and the second reaction zone II (lower end) in a
fixed bed reactor with an inner diameter of 16 mm, respectively.
The temperature was raised to 260.degree. C. under a 5 vol %
H.sub.2+95 vol % N.sub.2 atmosphere for 24 hours, and then the
temperature was adjusted to the reaction temperature (see Table 4
for details). The pressure of the reaction system was raised to 2
MPa with H.sub.2 and CO. The flow rate under standard conditions of
CO was 30 mL/min and the flow rate under standard conditions of
H.sub.2 was 60 mL/min. The results of the catalytic reaction were
shown in Table 4.
TABLE-US-00004 TABLE 4 Reaction results at different reaction
temperatures Percent Selectivity for products (%) Reaction
conversion Dimethyl Methyl Acetic temperature of CO (%) CO.sub.2
Methanol ether acetate acid Others 200 10.5 0.0 1.42 9.6 80.1 7.5
1.38 230 29.4 0.0 3.83 17.3 58.7 18.6 1.57 250 36.2 0.0 5.0 27.3
51.7 12.2 3.8 270 48.6 0.0 6.4 37.3 43.6 5.5 7.2 360 89.2 0.0 0 0
3.2 93.5 3.3
Example 2
[0057] Similar to the procedure of Example 1, the first reaction
zone was charged with 1 g of catalyst A, and the second reaction
zone was charged with 1 g of different solid acid catalysts (1-10#
and 12-16#, see Table 5), and the reaction temperature was
230.degree. C. Other conditions were the same as in Example 1. The
specific reaction results were shown in Table 5.
TABLE-US-00005 TABLE 5 Reaction results for different molecular
sieve catalysts Selectivity for products (%) Catalyst Percent
conversion Dimethyl Methyl Acetic No. of CO (%) CO.sub.2 Methanol
ether acetate acid Others 1# 26.8 0.0 0.23 9.78 72.40 17.14 0.45 2#
17.6 0.0 0.12 14.9 71.50 12.95 0.53 3# 13.5 0.0 0.05 8.70 85.78
5.26 0.21 4# 21.4 0.0 0.90 15.60 62.30 19.30 1.90 5# 15.8 0.0 2.80
68.70 3.20 0.00 28.5 6# 23.3 0.0 1.10 11.80 62.30 23.5 1.30 7# 25.8
0.0 0.90 8.65 63.80 24.53 2.12 8# 20.1 0.0 0.10 23.50 75.10 1.10
0.20 9# 17.6 0.0 0.38 31.60 63.10 4.53 0.39 10# 18.7 0.0 0.69 27.90
68.20 2.32 0.89 12# 31.2 0.0 0.81 10.30 68.70 19.8 0.39 13# 16.1
1.8 2.90 16.31 60.7 17.73 2.37 14# 17.3 5.6 0.63 14.42 59.6 19.18
0.57 15# 16.8 0.7 1.83 11.80 61.3 24.16 0.21 16# 15.9 0.3 0.56
13.38 60.2 25.05 0.51
Example 3
[0058] Similar to the procedure of Example 1, 1 g of copper-based
catalyst A and 1 g of molecular sieve catalyst 11# were
successively charged into the upper end and the lower end in the
fixed bed reactor with an inner diameter of 16 mm. The temperature
was raised to 260.degree. C. under a 5 vol % H.sub.2+95 vol %
N.sub.2 atmosphere for 24 hours, and then the temperature was
lowered to 230.degree. C. The pressure of the reaction system was
raised with H.sub.2 and CO (see Table 6). The flow rate under
standard conditions of CO was 30 mL/min and the flow rate under
standard conditions of H.sub.2 was 30 mL/min. The results of the
catalytic reaction were shown in Table 6.
TABLE-US-00006 TABLE 6 Reaction results at different reaction
pressures Percent Selectivity for products (%) Reaction conversion
Meth- Dimethyl Methyl Acetic pressure of CO (%) CO.sub.2 anol ether
acetate acid Others 1 21.3 0.0 6.93 22.1 53.7 15.6 1.67 5 33.4 0.0
2.7 12.9 63.7 19.6 1.10 8 36.8 0.0 0.1 8.8 71.7 19.1 0.3 15 53.8
0.0 0.1 1.8 95.7 2.2 0.2
Example 4
[0059] Similar to the procedure of Example 1, 1 g of copper-based
catalyst A and 1 g of molecular sieve catalyst 11# were
successively charged into the upper end and the lower end in the
fixed bed reactor with an inner diameter of 16 mm. The temperature
was raised to 260.degree. C. under a 5 vol % H.sub.2+95 vol %
N.sub.2 atmosphere for 24 hours, and then the temperature was
lowered to 230.degree. C. The pressure of the reaction system was
raised to 2 MPa with H.sub.2 and CO. The total flow rate under
standard conditions of CO and H.sub.2 was 60 mL/min. The ratios of
CO to H.sub.2 were shown in Table 7. The results of the catalytic
reaction were shown in Table 7.
TABLE-US-00007 TABLE 7 Reaction results under different ratios of
CO/H.sub.2 Percent Selectivity for products (%) CO/ conversion
Meth- Dimethyl Methyl Acetic H.sub.2 of CO (%) CO.sub.2 anol ether
acetate acid Others 0.5 32.3 0.0 6.6 45.5 38.3 7.5 2.1 2 18.7 0.0
2.71 10.7 62.2 21.8 2.59 3 9.6 0.0 0.98 3.5 78.3 16.6 0.62 8 3.6
0.0 0 1.5 94.8 3.5 0.2 10 2.5 0.0 0 1.4 94.9 3.6 0.1
Example 5
[0060] Similar to the procedure of Example 1, 1 g of catalyst and 1
g of molecular sieve catalyst 11# were successively charged into
the upper end and the lower end in the fixed bed reactor with an
inner diameter of 16 mm. The temperature was raised to 260.degree.
C. under a 5 vol % H.sub.2+95 vol % N.sub.2 atmosphere for 24
hours, and then the temperature was lowered to 230.degree. C. The
pressure of the reaction system was raised to 2 MPa. The ratio of
CO to H.sub.2 was 3, and the reaction atmosphere also contained
methanol and dimethyl ether. The total gas flow rate was 60 ml/min
under standard conditions. The specific ratios were shown in the
table. The selectivity of methanol and dimethyl ether was not
calculated in the reaction product. The results of the catalytic
reaction were shown in Table 8.
TABLE-US-00008 TABLE 8 Reaction results when the reaction
atmosphere contained methanol and dimethyl ether Meth- Di- CO anol
methyl Percent Selectivity for products (%) (ml/ (ml/ ether
conversion Methyl Acetic min) min) (ml/min) of CO (%) CO.sub.2
acetate acid Others 40 0 6.7 13.4 0 97.1 2.4 0.5 40 6.7 0 10.2 0
77.9 21.6 0.5
Example 6
[0061] Similar to the procedure of Example 1, 1 g of catalyst and 1
g of molecular sieve catalyst 11# were successively charged into
the upper end and the lower end in the fixed bed reactor with an
inner diameter of 16 mm. The temperature was raised to 260.degree.
C. under a 5 vol % H.sub.2+95 vol % N.sub.2 atmosphere for 24
hours, and then the temperature was lowered to setting 250.degree.
C. The pressure of the reaction system was raised by 2 MPa with
H.sub.2 and CO. The ratio of CO to H.sub.2 was 3. The total gas
flow rate and the results of the catalytic reaction were shown in
Table 9.
TABLE-US-00009 TABLE 9 Reaction results at different reaction space
velocities Selectivity for products (%) Total gas Percent Di- flow
rate conversion Meth- methyl Methyl Acetic (ml/min) of CO (%)
CO.sub.2 anol ether acetate acid Others 0 22.1 0.0 2.01 5.5 63.3
25.8 3.39 120 9.6 0.0 6.01 27.5 48.3 17.5 0.69 650 3.8 0.0 9.2 30.5
45.3 14.3 0.7
Example 7
[0062] Similar to the procedure of Example 1, different amounts
(see Table 10 in detail) of copper-based catalyst A and different
amounts (see Table 10 in detail) of catalyst 11# were successively
charged into the upper end and the lower end in the fixed bed
reactor with an inner diameter of 16 mm. The temperature was raised
to 260.degree. C. under a 5 vol % H.sub.2+95 vol % N.sub.2
atmosphere for 24 hours, and then the temperature was lowered to
setting 230.degree. C. The pressure of the reaction system was
raised to 2 MPa with H.sub.2 and CO. The flow rate under standard
conditions of CO was 30 mL/min and the flow rate under standard
conditions of H.sub.2 was 30 mL/min. The results of the catalytic
reaction were shown in Table 10.
TABLE-US-00010 TABLE 10 Reaction results with different catalyst
loading ratios Percent Selectivity for products (%) con- Di-
Catalyst version of Meth- methyl Methyl Acetic A 11# CO (%)
CO.sub.2 anol ether acetate acid Others 1 2 34.6 0.0 0.8 5.3 85.9
7.1 0.9 1 3 38.9 0.0 0.5 2.1 89.1 7.6 0.7 1 5 42.5 0.0 0.1 1.5 91.0
7.2 0.2 2 1 41.7 0.0 10.3 39.7 45.2 4.3 0.5 3 1 55.8 0.0 15.7 42.3
41.0 0.9 0.1
Example 8
[0063] The procedure was similar to that of Example 1, except that
the first reaction zone I and the first reaction zone II were
located in different fixed bed reactors. Specifically, referring to
FIG. 2, the reaction process was basically similar to the process
described in Example 1 with respect to FIG. 1. 1 g of copper-based
catalyst A and 1 g of carbonylation molecular sieve catalyst 11#
were successively charged into the first reactor and the second
reactor, respectively, wherein the inner diameter of the reactors
was 16 mm. The catalyst in the first reaction zone was heated to
260.degree. C. under a 5 vol % H.sub.2+95 vol % N.sub.2 atmosphere
for 24 hours, and then the temperature was lowered. The pressure of
the reaction system was raised to 2 MPa with H.sub.2 and CO. The
feed conditions in the first reaction zone were as follows. The
reaction temperature was 250.degree. C. The flow rate under
standard conditions of CO was 30 mL/min and the flow rate under
standard conditions of H.sub.2 was 60 mL/min. The effluent from the
first reaction zone entered the second reaction zone, while carbon
monoxide was added to the second reaction zone (standard conditions
30 mL/min), the effluent from the first reaction zone and the added
carbon monoxide entered the second reaction zone together. The
reaction results at the temperatures of 190, 210, 230, 280, and
300.degree. C. in the second reactor were shown in Table 11.
TABLE-US-00011 TABLE 11 Reaction results at different reaction
temperatures in the second reaction zone Reaction Percent
Selectivity for products (%) temper- con- Di- ature version of
Meth- methyl Methyl Acetic (.degree. C.) CO (%) CO.sub.2 anol ether
acetate acid Others 190 27.50 0.0 1.20 78.3 20.2 0.00 0.3 210 33.75
0.0 0.05 28.6 71.8 0.00 0.45 230 40.00 0.0 0.00 0.0 66.7 32.4 0.9
280 48.75 0.0 0.00 0.0 5.3 93.7 1.0 300 50.00 0.0 0.00 0.0 0.00
98.5 1.5
Example 9
[0064] The procedure was similar to that of Example 1, except that
the first reaction zone I and the first reaction zone II were
located in different fixed bed reactors. Specifically, referring to
FIG. 2, the reaction process was similar to the process described
in Example 1 with respect to FIG. 1.
[0065] 1 g of copper-based catalyst A and 1 g of carbonylation
molecular sieve catalyst 11# were successively charged into the
first reactor and the second reactor, respectively, wherein the
inner diameter of the reactors was 16 mm. The catalyst in the first
reaction zone was heated to 260.degree. C. under a 5 vol %
H.sub.2+95 vol % N.sub.2 atmosphere for 24 hours. When the
temperature was then lowered to 190, 220, 250, 280 and 300.degree.
C., the pressure of the reaction system was raised to 2 MPa with
H.sub.2 and CO. The feed conditions in the first reaction zone were
as follows. The flow rate under standard conditions of CO was 30
mL/min and the flow rate under standard conditions of H.sub.2 was
60 mL/min. The effluent from the first reaction zone entered the
second reaction zone, while carbon monoxide was added to the second
reaction zone (standard conditions 30 mL/min); the effluent from
the first reaction zone and the added carbon monoxide entered the
second reaction zone together. The reaction results at the
temperature of 230.degree. C. in the second reactor were shown in
Table 12.
TABLE-US-00012 TABLE 12 Reaction results at different reaction
temperatures in the first reaction zone Reaction Percent
Selectivity for products (%) temperature conversion Dimethyl Methyl
Acetic (.degree. C.) of CO (%) CO.sub.2 Methanol ether acetate acid
Others 190 12.00 0.0 0.0 0.00 0.00 99.5 0.5 220 31.00 0.0 0.05 0.00
0.00 99.3 0.45 250 43.33 0.0 0.00 0.00 73.6 25.5 0.9 280 53.60 0.0
0.00 15.27 82.85 0.88 1.0 300 63.50 0.0 0.00 32.37 65.43 0.70
1.5
Example 10
[0066] The procedure was similar to that of Example 1, except that
the first reaction zone I and the first reaction zone II were
located in different fixed bed reactors. Specifically, referring to
FIG. 2, the reaction process was similar to the process described
in Example 1 with respect to FIG. 1.
[0067] Copper-based catalyst A and carbonylation molecular sieve
catalyst 11# were successively charged into the first reactor and
the second reactor, respectively, see Table 10 for the catalyst
loading. The inner diameter of the reactors was 16 mm. The catalyst
in the first reaction zone was heated to 260.degree. C. under a 5
vol % H.sub.2+95 vol % N.sub.2 atmosphere for 24 hours. When the
temperature was then lowered to 230.degree. C., the pressure of the
reaction system was raised to 5 MPa with H.sub.2 and CO. The feed
conditions in the first reaction zone were as follows. The flow
rate under standard conditions of CO was 30 mL/min and the flow
rate under standard conditions of H.sub.2 was 60 mL/min. The
effluent from the first reaction zone entered the second reaction
zone, while carbon monoxide was added to the second reaction zone
(standard conditions 30 mL/min); the effluent from the first
reaction zone and the added carbon monoxide entered the second
reaction zone together. The reaction results at the temperature of
230.degree. C. in the second reactor were shown in Table 13.
TABLE-US-00013 TABLE 13 Reaction results at different reaction
temperatures in the first reaction zone Percent Selectivity for
products (%) Cata- con- Di- lyst version of Meth- methyl Methyl
Acetic A 11# CO (%) CO.sub.2 anol ether acetate acid Others 1 2
60.2 0.00 0.00 0.00 48.20 51.70 0.1 1 3 66.7 0.00 0.00 0.00 16.12
83.73 0.15 1 5 70.8 0.00 0.00 0.00 2.38 97.12 0.5 2 1 57.2 0.00
0.00 30.18 69.02 0.00 0.8 3 1 63.3 0.00 0.00 40.04 59.06 0.00
0.9
Example 11
[0068] The procedure was similar to that of Example 1, except that
the first reaction zone I and the first reaction zone II were
located in different fixed bed reactors. Specifically, referring to
FIG. 2, the reaction process was similar to the process described
in Example 1 with respect to FIG. 1.
[0069] 1 g of copper-based catalyst B and 1 g of carbonylation
molecular sieve catalyst 11# were successively charged into the
first reactor and the second reactor, respectively, wherein the
inner diameter of the reactors was 16 mm. The catalyst in the first
reaction zone was heated to 260.degree. C. under a 5 vol %
H.sub.2+95 vol % N.sub.2 atmosphere for 24 hours. When the
temperature was then lowered to 230.degree. C., the pressure of the
reaction system was raised to 5 MPa with H.sub.2 and CO. The feed
conditions in the first reaction zone were as follows. The flow
rate under standard conditions of CO was 30 mL/min and the flow
rate under standard conditions of H.sub.2 was 60 mL/min. The
effluent from the first reaction zone entered the second reaction
zone, while carbon monoxide was added to the second reaction zone
(standard conditions 30 mL/min); the effluent from the first
reaction zone and the added carbon monoxide entered the second
reaction zone together. The reaction results at the temperature of
230.degree. C. in the second reactor were shown in Table 14.
TABLE-US-00014 TABLE 14 Reaction results when catalyst B was loaded
in the first reaction zone Percent con- Selectivity for products
(%) version of CO Meth- Dimethyl Methyl Acetic (%) CO.sub.2 anol
ether acetate acid Others 40.2 29.2 0.00 0.00 69.3 0.8 0.7
[0070] The present invention has been described in detail above,
but the present invention is not limited to the specific
embodiments described herein. Those skilled in the art can
understand that other changes and modifications can be made without
departing from the scope of the invention. The scope of the
invention is defined by the appended claims.
* * * * *